Copolymer of vinyl pyrrolidone and vinyl acetate as aerosol hair spray



United States Patent 3,171,784 COPOLYMER 0F VlNYL PYRROLIDDNE AND VINYLACETATE AS AEROSOL HAIR SPRAY Daniel B. Witwer, Montclair, Ni, assignorto General Aniline & Film orporation, New York, N.Y., a corporation ofDelaware No Drawing. Filed Nov. 9, 1956, Ser. No. 621,206

13 Claims. (Cl. 167-87) The present invention relates to aerosol filmforming compositions and particularly to improved hair waving andsetting compositions.

There are numerous preparations available for the waving and setting ofhuman hair. Most of them are based on aqueous film forming solutions.The principal ingredient of such Solutions is either a natural gum orresin or synthetic resins which upon evaporation of the liquid mediumdeposits a film or coating. In addition to natural gums and resins,various alcohol soluble proteids, such as gliadin, zein, and the like,gelatin, a mixture of egg albumen, casein, and sodium silicate,inorganic resinous compounds obtained by treating anhydrous monosodiumphosphate with borax, and various water soluble polymeric acrylic acidderivatives have been employed.

Since natural gums, such as, for example, karaya gum, salts of alginicacid, gum acacia, etc., flake off, dry hard, and impart an undesirablestiffness and brittleness, their use has been replaced by water solublesynthetic resins, such as those obtained by incomplete saponification orhydrolysis of polymeric acrylic and a-alkacrylic esters and amides. Thedisadvantage of waving fluid or hair dressing preparations containingsuch resins is that the preparations cannot tolerate bleaching agentswithout the presence of ammonia, or an ammonium salt, such as ammoniumcarbonate. The latter compounds have the tendency to imparthydroscopicity to the resinous film or coating after evaporation of theliquid medium or carrier. As a result, the film or coating becomes tackyand develops a greasy feel. Moreover, depending upon the nature of thewater soluble polymeric acrylic acid derivative, some derivatives havethe tendency of rubbing loose and falling off the hair in the form ofsmall flakes resembling dandruff, while others require alkaline mediafor easy removal from the hair. It is well recognized among hairstylists and beauticians that ammonia has distinct hair stiffeningcharacteristics whereby the fibers of the hair are attacked with asubsequent altering of its natural life.

Alcoholic solutions of shellac have also been employed and are currentlysold in limited amounts in a Freon System. The disadvantage of shellacis that it must be solubilized with alkaline media, such as caustic sodaor caustic potash for preparation of the solution prior to formulationin a pressurized can. Moreover, the same alkaline media must be employedto remove it from the hair.

Various synthetic polymers have been tried for use in hair groomingpreparations, but have not been practical because of their solubilitycharacteristics, i.e., they are not suitable for application and/orremoval from the natural hair filaments. For example, gums and manypolymers are not soluble in aerosol propellants and hence cannot be usedin aerosol sprays. Also, many polymers are affected by changes in therelative humidity and the hair varies from a stiff, boardy feel to asticky feel. Of the several polymers available, polyvinylpyrrolidone(more popularly termed PVP) is outstanding and currently employed inaerosol hair grooming preparations. When a PVP alcohol solution isapplied in an aerosol system to human hair under a relative humidity ofless 3,171,784 Patented Mar. 2, 1965 than 50%, the tendency of theresulting film to tackiness is substantially decreased. As a resultthereof the preparation is acceptable by all consumers. However, whenthe relative humidity is above 50%, and particularly at humidatmospheres, films of PVP, sprayed from an aerosol system, pick upconsiderable moisture. The moisture is retained and results in a tackyfilm. In view of this property, the aerosol preparation is extremelyundesirable where a dry hair condition is required as is the case withmost users, especially women. The equilibrium water content of PVPdepends upon the relative humidity of the atmosphere. The moisturecontent varies in a linear fashion with relative humidity, and theequilibrium percentage of moisture is about one-third of the relativehumidity. Thus, if PVP is exposed to a relative humidity of 50%, themoisture pickup is approximately one-third of the relative humidity andtherefore the resulting film contains about 17% moisture. To overcomethe unique hygroscopicity of PVP, it has been suggested to employdetackifying agents such as shellac, cellulose acetate-propionate, etc.The former yields films which become opaque at high humidities, and thelatter yields a film insoluble in ethyl alcohol.Carboxy-methylcellulose, cellulose acetate, methyl methacrylate polymer,polyvinyl formal, etc., are not effective as detackifiers underconditions of extremely high humidities.

It is an object of the present invention to provide improved,hairwaving, hair setting, and hair dressing compositions which are freefrom the foregoing disadvantages and which, in addition, possess new anddesirable properties.

Other objects and advantages will become apparent from the followingdescription.

We have found that a composition possessing new and desirable propertiesfor application to human hair comprises an alcoholic solution of acopolymer of an N-vinyl pyrrolidone and a vinyl ester, which is usefulin aerosol sprays, atornizers or can be applied directly to hair. Suchsolution, in combination with an aerosol propellant such as, forexample, Freon 11, 12, 112, 113, 114, Freon C-316 and mixtures thereof,when applied to human hair, yields a glossy film which is substantiallytack-free under normal conditions of relative humidity. The resultingfilm when exposed to a relative humidity of 50% and higher contains nomore than about 13% moisture and is sufliciently water-sensitive so thatit can be removed from the hair by a single washing. The equilibriumpercentage of moisture of the copolymer is not more than one-fourth ofthe relative humidity. Thus, if the copolymer or film thereof is exposedto a relative humidity of 52%. the resulting film contains about 13.4%of one-fourth of the relative humidity. Thus, if the copolymer, it isnot necessary to employ de-tackifying agents.

We have further found that in order to achieve the foregoing desirableproperties it is necessary to employ from 30 to 60% by weight of a vinylpyrrolidone monomer and from 40 to 70% by weight of a monomeric vinylester. When such weight-percent ratios are employed in preparing thecopolymer, films resulting therefrom maintain suflicientwater-sensitivity so that they can be removed from the hair. Thecopolymers in such ratios are also soluble in the lower alcohols suchas, for example, methanol, ethanol, isopropanol and the like, and withall of the aforementioned Freons and mixtures thereof. In cases where itis desirable to produce a hair grooming preparation or industrialcoating compositions which lack water-sensitivity under all conditionsof relative humidity, and may require several washings before the filmis removed, the weight-percent ratio of the monomers may be increasedfrom 10 to 50% of a polymerizable vinyl ester 3 and from 50 to 90% byweight of a polymerizable N-vinyl pyrrolidone. Thus, it becomes clearlyevident that the ratio of polymerizable monomers used may range widelyto yield water-sensitive to water-insoluble copolymers, both of whichare soluble in alcohol and 'fluorinated alkane aerosol propellants. Forhair grooming preparations, we prefer to employ copolymers in which themonomers are in the ratio of 30:60 of the N-vinyl pyrrolidone and 40 to70% by weight of the vinyl ester. In these proportions a copolymer isobtained which is readily soluble in the lower alcohols and dissolves inall of the currently employed Freons and mixtures thereof to yield ahair grooming preparation, the films of which do not become opaque ortacky at high humidities. The resulting films are glossy, tack-free andreadily removed by a water wash or a water rinse.

The copolymers utilized in preparing the film forming and hair groomingcompositions of the present invention are readily prepared bycopolymerizing the two monomers in the aforementioned weight-percentratio by conventional means or in lower alcohol solvent so that thesolution thereof can be used directly in the preparation of an aerosol.The method of copolymerization may be either in bulk, in emulsion or insolution. Instead of a lower alcohol as a solvent, the monomers may bedissolved or dispersed in water or an organic solvent such as benzene,dioxane acetone, methyl ethyl ketone, ethylene dichloride or mixture ofsuch organic solvents. The solution or dispersion of the two monomers,in then heated in the usual manner preferably in the absence of air(nitrogen blanket) in the presence of a polymerizing catalyst such asorganic peroxides, peracids, hydroperoxides, i.e., benzoyl peroxide,lauryl peroxide,; tertiary butyl perbenzoate, hexoyl peroxide, methylethyl ketone peroxide, a-azodiisobutyronitrile and the like.

As illustrative examples of N-vinyl pyrrolidones which may becopolymerized in the aforestated concentrations with a vinyl ester, thefollowing may be mentioned:

As. illustrative examples of polymerizable vinyl esters, the followingmay be mentioned:

Vinyl acetate Vinyl glycolate Vinyl chloride Vinyl formate Vinylpropionate Vinyl butyrate The copolymers, prepared with theaforementioned monomers as herein described, correspond to a range of aFinkentscher K value of to 60. These valueswapply to both thewater-sensitive and water-soluble copolymers. K value as used herein isdefined by the following implicit function of Fikentscher,Cellulosechemie, 13, 60 (1932):

0.001K+ 0.O00075K Relative viscosity 10C 1 000151) A definition of Kvalue is also given in Modern Plastics, 23, 157-161 (November 1945). I I

The invention will be described in greater length in conjunction withthe following examples. It is to be understood, however, that theseexamples are merely illustrative and are not intended that the scope ofthe invention be limited to them and to the details set forth herein.

4 EXAMPLE 1 A one-liter, three-necked flask equipped with stirrer,reflux condenser and a thermometer was charged with grams of vinylacetate, distilled, 225 grams of N-vinyl-2- pyrrolidone, distilled, and300 ml. of Z-butanone. The flask was heated to 75 C. with stirring for 5minutes. After 5 minutes, 3 grams of 2,2'-azodiisobutyronitriledissolved in 37.5 ml. of 2-butanone was added to the flask. The flaskwas stirred and maintained at,70 C. for a total of 12 hours. The productwas recovered by evaporating the Z-butanone leaving a solid, white,clear polymer containing 75% N-vinyl-2-pyrrolidone and'25% vinylacetate. The polymer dissolved in Z-butanone gave a Fikentscher K valueof 17.

EXAMPLE 2 A two-liter, three-necked, ground-joint, Pyrex flask equippedwith two Allihn condensers, mechanical stirrer with half-moon blade,thermometer, and a nitrogen-inlet tube was charged with 139.0 grams (175ml.) of denatured ethanol, 83.25 grams (0.75 mole) ml.) of distilledN-vinyl-Z-pyrrolidone, 64.57 grams (0.75 mole) (69.3 ml.) of vinylacetate, distilled, and 0.75 gram of 2,2'-azodiisobutyronitriledissolved in '30 ml. of denatured ethanol. The flask was flushed withnitrogen and the inlet rate adjusted to about 3060 bubbles per minute.The flask was heated on a steam bath of 70 C. The steam was turned offand the catalyst was added via the condenser.

. The temperature dropped to 56 C. The steam was then when correctedindicates 60% bound N-vinyl-2-pyrrolidone and 40% bound vinyl acetate bydifference. Analysis for volatiles gave 4.6%. Analysis for free monomergave 0.01% calculated as N-vinyl-2-pyrrolidone.

EXAMPLE 3 Into an Autoclave Engineer steel autoclave were placed 73.80grams of N-vinyl-2-pyrrolidone, 20.80 grams of vinyl chloride, 87.5grams of 2-butanone and 0.410 gram of 2,2'-azodiisobutyronitrilecatalyst. The autoclave was sealed and heated to 60 C. and stirred withan enamel coated stirrer for 20 hours. The autoclave was cooled to roomtemperature and vented into a Dry Ice trap. The trap did not gain inweight. The contents of the autoclave were poured into a tared Pyrexdish and placed in an air stream to evaporate the solvent. After 18hours a thick syrup remained. The thick syrup was placed in a desiccatorunder vacuum and the remaining solvent removed. The polymer obtained wasa straw colored, friable material which was easily pulverized withmortar and pestle. Analysis for Volatiles indicated that the actualyield of dry polymer was 93% of the theoretical yield. Analysis for theN content bound in the polymer indicated N-vinyl-2-pyrrolidone contentand 10% vinyl chloride content by difference. The polymer gave aFikentscher K-value of 22 in water.

EXAMPLE 4 Into'a metal aerosol can partially submerged in a solid carbondioxide acetone bath were condensed 40 grams of Freon 12, 40 grams ofFreon 11, and to this was added 20 grams of an alcoholic solutioncontaining a copolymer of N-vinyl-Z-pyrrolidone and vinyl acetate(Example 2). A nozzle and valve assembly was attached to the can and theentire assembly was held together in a brass cage. The can was checkedfor leaks by submerging in water. The aerosol sprayer was allowed towarm to room temperatu're. Glass panels were sprayed giving films whichdried almost immediately to an odor-free, clear, somewhat flexible film.The films were not tacky. Also, the films when rubbed with a wet fingerwere not as sensitive as films containing polyvinylpyrrolidone. Thecompounded aerosol was used to spray hair and allowed to dry. The filmresulting on the hair brightened and gave the hair a pleasing appearanceand retained the shape and condition that the hair was held in whilebeing sprayed. That is to say, it is useful in retaining artificialcurls in hair.

Two manufacturing steps were saved by using the alcoholic solution: (1)the normal spray drying step to recover the polymer, and (2) thedissolving of the polymer into ethanol prior to the preparation of theaerosol.

EXAMPLE 5 Into a three-necked, one-liter Pyrex flask equipped with anAllihn condenser, a thermometer, a mechanical stirrer, and a nitrogeninlet was charged 60.0 grams of distilled N-vinyl-2-pyrrolidone, 40.0grams of distilled vinyl propionate and 200 grams of anhydrous ethanol.The flask was flushed with nitrogen and the inlet rate of the gasadjusted to about 30 bubbles per minute. The flask was heated andstirred for 30 minutes at 60 C. At this point 0.1 gram of2,2-azodiisobutyronitrile was added as the catalyst. The flask wasmaintained at 80 C. and was stirred for a total of 12 hours. At thispoint the reaction mixture gave an analysis of 3 residual unsaturation.

0.1 gram of 2,2azodiisobutyronitrile was added and the flask was heatedfor an additional 3 hours. The prodnot was recovered for /2 of thereaction mixture by vacuum stripping. The product consisted of a white,friable, transparent polymer. The remaining half of the reactionsolution was bottled for use in its original condition.

Analysis indicated the polymer contained 60% vinylpyrrolidone and 40%vinyl propionate. A sample of the dried polymer gave a FikentscherK-value of 33 in 2- butanone.

EXAMPLE 6 Into a three-necked flask equipped with an Allihn condenser, athermometer, a nitrogen inlet, and a mechanical stirrer was charged 55.0grams of N-vinyl-2-pyrrolidone, 45.0 grams of vinyl propionate and 200grams of Z-butanone. The flask was flushed with nitrogen and the inletrate of the gas was adjusted to about 30 bubbles per minute. The flaskwas stirred and heated to 60 C. for 30 minutes. At this point 0.1 gramof 2,2'- azodiisobutyronitrile was added as the catalyst. The flask wasstirred and maintained at 30 C. for a total of 12 hours. The polymer wasrecovered from the reaction solution by drying in a vacuum desiccatorfor 24 hours at less than 0.2 mm. of mercury vacuum.

The white, brittle, translucent polymer was analyzed and the analysisindicated that it contained 55% vinylpyrrolidone and 45% vinylpropionate. A sample of the dried polymer gave a Fikentscher K-value of30 in 2- butanone.

EXAMPLE 7 Into a 4 ounce aerosol can were condensed 25 grams oftrichloromonofluoromethane and 25 grams of dichlorodifluoromethane. Tothis was added 6 grams of the reaction solution from Example 5, and anozzle assembly was attached to the can and the can allowed to warm toroom temperature.

The filled aerosol was used to spray glass panels 8 inches by 10 inches,21 hank of human hair and a head of human hair. The panels containedcontinuous film of the polymer and it was noticed they dried rapidly toa tack-free, transparent, odorless film. The hair sprayed with theaerosol contained a clear, transparent coating which brightened theappearance of the hair. It was observed that when the head of human hairwas sprayed and allowed to dry that the polymer did show hair fixativeproperties, that is to say, the hair coated with the polymer tended tohold the shape imposed upon it.

EXAMPLE 8 Into a glass aerosol compatability tube (obtained from FischerPorter of Hatboro, Pennsylvania) was condensed, when the tube was cooledin an acetone solid carbon dioxide bath, 20 grams oftrichloromonofluoromethane and 20 grams of dichlorodifluoromethane. Tothe tube Was added 5 grams of a 50% solution of the polymer from Example6 dissolved in anhydrous ethanol. The compatibility tube was sealed anda nozzle assembly attached to it. The completed aerosol in thecompatibility tube was allowed to warm to room temperature and it wasobserved that a solution of all the ingredients took place.

The completed aerosol was used to spray a glass panel 8 inches by 10inches and a head of human hair. A quick drying, continuous, clear,tough film was observed. It was observed that the hair was held in placeby the dried coating of polymer. The polymer was observed to have hairfixing properties.

EXAMPLE 9 Into a metal aerosol can partially submerged into an acetonesolid carbon dioxide cooling bath was condensed 35 grams oftrichloromonofluoromethane, and 35 grams of dichlorodifluoromethane. Tothe can was added 10 grams of a 50% solution obtained from Example 2. Anozzle assembly was attached to the can and the can was sealed in abrass cage. The completed aerosol can was allowed to warm to roomtemperature.

The aerosol was used to spray a human finger and allowed to dry. It wasobserved for an area of about 2 square inches a clear, continuous filmcovered the finger. This cover could be used in place of the ordinarycloth tape bandage. The aerosol was used to spray a human finger whichhad a slight topical cut (about A: inch long and inch deep) and it wasobserved that a film was obtained on the finger. The finger was sprayedafter the wound had closed by coagulation of the blood. A slightsmarting sensation was noticed.

The coating did offer protection to the wound and did not rub off ifcare was taken not to vigorously scrub the finger with water.

EXAMPLE 10 As noted in Example 4 of application, Serial No. 535,262,filed on September 19, 1955, there was prepared a complex of a copolymerof N-vinyl-2-pyrrolidone and vinyl acetate and pulverized granulariodine. Also, as noted, the iodine complex was treated at 55 C. for 4hours and after heat treatment the complex analyzed 1.4% availableiodine.

Into a metal aerosol can partially submerged into a solid carbon dioxideacetone bath was condensed 40 grams of trichloromonofiuoromethane and 40grams of dichlorodifluoromethane. To the can was added 5 grams of the50% solution from Example 2 and 2 grams of the iodine polymer complexdescribed above. An aerosol nozzle assembly was attached to the can andthe can was sealed in a brass cage. The completed aerosol was allowed towarm to room temperature.

The aerosol was used to spray a human finger and the coating obtainedwas allowed to dry. A slightly brown, continuous, protective coating wasobtained on about 1 square inch of the finger surface. The coatingadhered well to the finger and was not sticky and did not rub oif whenmassaged with a dry hand. It was observed the finger could be flexedwithout cracking or breaking the continuous film.

The aerosol was used to spray a finger which had a slight surface cut(about inch long and about ,4 inch deep). The finger was sprayed afterthe blood had coagulated. After the film dried, it was observed that thewounded area was covered by a light brown film.

7 EXAMPLE 11 Into a one-liter beaker was placed 500 cc. of anhydrousethanol, 40 grams of. reaction solution from Example 2 and 10 grams ofthe iodine complex described in Example 10. The contents of the flaskwas stirred and a solution resulted which was brownish in color andwhich when cast onto a glass plate dried rapidly.

The solution was used to prepare an antiseptic area on human skin byapplying a coating with a brush or similar instrument and allowing it todry.

EXAMPLE 12 The solution given in Example 11 was used to prepare a pairof antiseptic gloves or coatings on human hands. The hands werecarefully Washed and dried. The hands were then submerged into thesolution and withdrawn and allowed to dry. A continuous light browncoating was obtained on the portion of the hands which had beensubmerged into the solution. The antiseptic coating functioned and tookthe place of the common surgeons rubber gloves. Any small area of thecontinuous film coating the hands could be easily repaired if damaged bybrushing on enough of the solution to cover the damaged area andallowing it to dry to a film. The hands could be flexed and used and nocracking or peeling of the film was observed. 1 V

In order to ascertain the criticality of the weight-percent ratio of themonomers in the copolymer, several copolymers were made in which theN-vinyl-Z-pyrrolidone content ranged from 20 to 60% by weight. Films ofsuch copolymers were both air dried and heated and their dissolvingtendencies in water observed. The results obtained are shown in thefollowing table:

Comparison of VP/ VA copolymers FILMS IMMERSED IN WATER Air-driedFilms-Time for Film t 1 Soluble.

2 Partly sol. 2 Do.

D0. 1 Not dispersible.

l The film of copolymer was coated on a glass slide and air dried.

2 VP =N-vinyl-Z-pyrrolidone/VA=vinyl acetate.

3 Solutions (0.5% in water) and shaken for 1 hr.

From the foregoing table it becomes clearly manifest that theWeight-percent ratio of the monomers is very critical and thatcopolymers outside the aforementioned desired ratio will lead to filmswhich are insoluble, thereby requiring several vigorous washings beforeremoval. In other words, the desired ratio in which all of theaforementioned desired properties are found is in 30 to 60% by weightN-vinyl-Z-pyrrolidone and from 40 to 70% by weight of vinyl ester.

I claim: V

l. A sprayable film forming preparation substantially tack-free undernormal conditions of relative humidity consisting essentially of acopolymer of 30-60% by weight of N-vinylpyrrolidone and 40-70% by weightof a vinyl ester in solution of a mixture of a low boiling aliphaticalcohol of 1 to 3 carbon atoms and at least one aerosol propellant fromthe class of liquified chlorofiuoro hydrocarbons of one to. two carbonatoms, the said mixture being present in suficient amount to dissolvethe said copolymer and render it sprayable, the said'vinyl ester beingcharacterized by the following formula:

CHZ=RCHR wherein R represents a member selected from the classconsisting of chlorine, formyl, acetyl, hydroxyacetyl, propionyl andbutyryl. 2. A sprayable hair grooming preparation substantiallytack-free under normal conditions of relative humidity and havingwater-solubility 'for removal from the hair consisting essentially of acopolymer of N-vinylpyrrolidone and a vinyl ester in solution of a lowboiling aliphatic alcohol of 1 to 3 carbon atoms and at least oneaerosol propellant from the class of liquified chloro-fiuorobydrocrabons of one to two carbon atoms, the said alcohol and propellantbeing present in sufficient quantities to dissolve the said copolymerand render it sprayable, said copolymer having a Fikentscher K value of15 to 60 and consisting of from about 30 to about 60% by weight ofN-vinylpyrrolidone and from about 40 to 70% I by weight of a vinylester'having the following formula:

CH =CHR wherein R represents a member selected from the class consistingof chlorine, formyl, acetyl, hydroxy acetyl, propionyl and butyryl.

3. A sprayable hair grooming preparation according to claim 2 whereinthe aerosol propellant is a mixture of trichloromonofiuoromethane anddichlorodifluromethane.

4. A sprayable hair grooming preparation according to claim 2 where theaerosol propellant is trifluoromethylchloride.

5. A sprayable hair grooming preparation according to claim 2 whereinthe copolymer is a copolymer of 30% by weight of N-vinylpyrrolidone and70% by weight of vinyl acetate.

6. The process of keeping human hair in place which comprises sprayingsaid hair with a fine mist dispensed fro-m an aerosol container whoseessential contents consist of a volatile, chloro-fluoro-substitutedlower aliphatic hydrocarbon propellent having dissolved therein acopolymer consisting of about 50% vinyl pyrrolidone and about 50% ofvinyl acetate, and a low boiling aliphatic alcohol of 1 to 3 carbonatoms.

7. The process of keeping human hair in place which comprises sprayingsaid hair with a fine mist dispensed from an aerosol container whoseessential contents consist of a volatile, chloro-fluoro-substitutedlower aliphatic hydrocarbon propellent having dissolved therein acopolymer consisting of about 30-90% vinyl pyrrolidone and about lO-70%by weight of vinyl acetate, and ethyl alcohol.

8. A sprayable film-forming preparationsubstantially tack-free undernormal conditions of relative humidity consisting essentially of acopolymer of about 30 to about percent by weight of N-vinyl pyrrolidoneand from about 25 to about 70 percent by weight of a vinyl ester insolution of a mixture of a low-boiling aliphatic alcohol of l-3 carbonatoms and at least one aerosol propellant from the group of liquifiedchloro-fluoro hydrocarbons of from 1 to 2 carbon atoms, the said mixturebeing present in sufiicient amount to dissolve the said copolymer andrender it sprayable, the said vinyl ester being of the formula:

CH2=CHR V wherein R is a member of the group consisting of chloro,formyl, acetyl, hydroxy acetyl, propionyl and butyryl.

9. A sprayable film-forming preparation substantially tack-free undernormal conditions of relative humidity consisting essentially of acopolymer of from about 30 to about percent by weight of N-vinylpyrrolidone and from about 10 to about 70 percent by weight of a vinylester in solution ofa mixture of a low-boiling aliphatic alcohol of l3carbon atoms and at least one aerosol propellant from the group ofliquified chloro-fluoro hydrocarbons of l to 2 carbon atoms, the saidmixture being present in sufficient amount to dissolve the saidcopolymer and render it sprayable, the said vinyl ester being of theformula:

CH CHR wherein R is a member of the group consisting of chloro, formyl,acetyl, hydroxy acetyl, propionyl and butyryl.

10. A sprayable film-forming preparation substantially tack-free undernormal conditions of relative humidity consisting essentially of acopolymer of from about to about 60 percent by weight of N-vinylpyrrolidone and from about to about 70 percent by weight of a vinylester in solution of a mixture of a low-boiling aliphatic alcohol of 1-3carbon atoms and at least one aerosol propellant from the group ofliquified chloro-fluoro hydrocarbons of 1 to 2 carbon atoms, the saidmixture being present in suflicient amount to dissolve the saidcopolymer and render it sprayable, the said vinyl ester being of theformula:

CH =CHR wherein R is a member of the group consisting of chloro, formyl,acetyl, hydroxy acetyl, propionyl and butyryl.

11. A sprayable hair-grooming preparation substantially tack-free undernormal conditions of relative humidity and having water solubility forthe removal from the hair consisting essentially of a copolymer ofN-vinyl pyrrolidone and a vinyl ester in solution of a low-boilingaliphatic alcohol of 1-3 carbon atoms and at least one aerosolpropellant from the group of liquified chlorofluoro hydrocarbons of 1 to2 carbon atoms, the said alcohol and propellant being present insufiicient quantities to dissolve the said copolymer and render itsprayable, said copolymer having a Fikentscher K value of 15 to andconsisting of from about 30 to about 75 percent by weight of N-vinylpyrrolidone and from about 25 to about percent by weight of a vinylester having the formula:

CH CHR wherein R is a member of the group consisting of chloro, formyl,acetyl, hydroxy acetyl, propionyl and butyryl.

12. A sprayable hair-grooming preparation substantially tack-free undernormal conditions of relative humidity and having water solubility forremoval from the hair, consisting essentially of a copolymer of N-vinylpyrrolidone and vinyl acetate in solution of a low-boiling aliphaticalcohol of 1-3 carbon atoms and at least one aerosol propellant from thegroup of liquified chlorofluoro hydrocarbons of 1 to 2 carbon atoms,said copolymer having a Fikentscher K value of 15 to 60 and consistingof from about 30 to about percent by weight of N-vinyl pyrrolidone andfrom about 25 to about 70 percent by weight of vinyl acetate, the saidmixture being present in sufficient amount to dissolve the saidcopolymer and render it sprayable.

13. The process of keeping human hair in place which comprises sprayingsaid hair with a fine mist dispensed from an aerosol container whoseessential contents consist of a volatile chloro-fluoro substituted loweraliphatic hydrocarbon propellant having dissolved therein a copolymerconsisting of from about 30 to about percent by weight of N-vinylpyrrolidone and from about 10 to about 70 percent by weight of a vinylester having the formula:

CH =CHR wherein R is a member of the group consisting of chloro, formyl,acetyl, hydroxy acetyl, propionyl and butyryl.

References Cited by the Examiner UNITED STATES PATENTS 2/50 Werntz. 1/54Morner et a1. 26085.7

OTHER REFERENCES JULIAN S. LEVITT, Primary Examiner.

W. B. KNIGHT, M. O. WOLK, Examiners.

1. THE PROCESS OF KEEPING HUMAN HAIR IN PLACE WHICH COMPRISES SPRAYINGSAID HAIR WITH A FINE MIST DISPENSED FROM AN AEROSOL CONTAINER WHOSEESSENTIAL CONTENTS CONSIST OF A VOLATILE, CHLORO-FLUORO-SUBSTITUTEDLOWER ALIPHATIC HYDROCARBON PROPELLENT HAVING DISSOLVED THEREIN ACOPOLYMER CONSISTING OF ABOUT 30-90% VINYL PYRROLIDONE AND ABOUT 10-70%BY WEIGHT OF VINYL ACETATE, AND ETHYL ALCOHOL.